III.

HALOGENOACIZI
R

CH

COOH

X = F, Cl, Br, I

Preparare
1. Halogenarea direct

CH3 COOH

+ Cl2
-HCl

ClCH2 COOH
Acid cloroacetic

+ Cl2
-HCl

Cl2CH COOH
Acid dicloroacetic

Conditii: Temp. sau h - mecanism homolitic

Omologi - amestecuri

+ Cl2
-HCl

Cl3C COOH
Acid tricloroacetic

2. Reacia Hell-Volhard-Zelinski
H2O

R CH2 COOH

+ Br2
Prosu

-HBr

R CH COBr
Br

R'OH
-HBr

R CH COOH
Br
R CH COOR'
Br

Orientarea n poziia a halogenrii este determinat de vecintatea grupei COBr

3. Halogenarea esterului malonic i a derivaillor si alchilai

Conditii: clorur de sulfuril (SO2Cl2), brom sau iod i acid iodic

COOR
R HC
COOR

Br2
- HBr

COOR
R C
Br COOR

+ H2O

COOH
R C

-CO2

Br COOH

R CH COOH
Br

4. Oxidarea aldehidelor halogenate

Cl3C CH O

HNO3

Cloral

Cl3C COOH
Acid tricloroacetic

5. Reacii de dublu schimb

Cl3C COOH + 3 NaF

F3C COOH + 3 NaCl

6. Adiia de acizi halogenai la acizi carboxilici nesaturai

CH3 CH CH COOH + HBr

CH3 CH CH2 COOH

Br Acid 3-bromobutiric

Acid crotonic

HOOC CH CH COOH + HBr

HOOC CH CH2 COOH

Br Acid bromosuccinic

Acid fumaric (sau maleic)

7. Metode speciale
Cl2C CH Cl
Tricloroetilena

1/2 O2

Cl2C CH Cl
O

Epoxid
(intermediar instabil)

izomerizare

Cl2CH COCl
Clorura acida a
acidului dicloroacetic

 Reactivitate

Aciditatea halogeno-acizilor

aciditatea halogenoacizilor este mai mare dect a acizilor carboxilici corespunztori

- efectul inductiv, atrgtor de electroni al halogenului
- efectul cel mai puternic l produce atomul de fluor
O

O
X

HC

H2O

HC

OH

Constante de aciditate ale acizilor acetici clorurai:

Acidul
Formula chimic
Acetic
CH3-COOH
Cloroacetic
ClCH2-COOH
Dicloroacetic
Cl2CH-COOH
Tricloroacetic
Cl3C-COOH
Constante de aciditate ale acizilor halogeno-acetici:
Acidul
Formula chimic
Iodoacetic
I-CH2COOH
Bromoacetic
Br-CH2COOH
Cloroacetic
Cl-CH2COOH
Fluoroacetic
F-CH2COOH

H3O+

O-

pKa
4.74
2.85
1.48
0.77

pKa
3.10
2.90
2.85
2.65

 Reacia de hidroliz

Cl-CH2COOH
Acid cloroacetic

+ H2O
- HCl

CH3 CH COOH

+ H2O
- HCl

HO CH2 COOH
Acid glicolic

SN2
CH3 CH COOH
OH

Cl

Acid cloropropionic

Acid lactic

Stereochimie
Inversia configuraiei n substituia nucleofil la carbonul saturat.
Inversia Walden (1895)
SN2
R1

R1
Nu

R2
R3

Nu

C
R2

R1
X

Nu

C
R2

R3

R3

Hidroliza enantiomerilor acidului clorosuccinic

H
C COOH

(-) HOOC CH2

Cl
H
C COOH

Ag2O

(-) HOOC CH2

Acid malic (-) OH

Pastrarea
configuratiei

KOH
PCl5

(+) HOOC CH2

Acid malic (+)
Ag2O

PCl5
KOH

(+) HOOC CH2

H
H2C

Cl

COOH

H
Cl
C COOH

Inversia
configuratiei

OH
C COOH

-Cl

O
C

H HC
2

OH

COOH

-Lactona

Prima inversie

C
H
OH
H2C
COOH
A doua inversie

IV.1. Hidroxiacizi

HO CH2 COOH

CH3 CH COOH

HOOC CH2 CH COOH

OH

OH
Acid glicolic

C6H5 CH COOH C6H5 CH COOH

OH

Acid malic

Acid lactic

CH2OH

COOH
H C OH
H C OH

CH2 COOH
HO C COOH
CH2 COOH

COOH
Acid mandelic

Acid tropic

Acid mezo-tartric

Acid citric

 Preparare
1. Hidroliza halogenoacizilor

Cl-CH2COOH
Acid cloroacetic

+ H2O
- HCl

CH3 CH COOH

HO CH2 COOH
Acid glicolic

+ H2O
- HCl

CH3 CH COOH
OH

Cl

Acid cloropropionic

Acid lactic

2. Reducerea acizilor aldehidici i cetonici

CH3 C COOH

2 [H]

CH3 CH COOH
OH

Conditii normale de reducere amestec racemic

Catalizatori sau agenti de reducere optic activi- reducere enantioselectiva

3. Reacia de desaminare a aminoacizilor

CH3 CH COOH
NH2
-Alanina

HONO

CH3 CH COOH + N2 + H2O

OH

4. Adiia acidului cianhidric a aldehide i cetone

HCN

C6H5 CH O

C6H5 CH CN

H2O
H

C6H5 CH COOH + NH3

OH

OH
Nitril mandelic

Benzaldehida

CH2 Cl

CH2 Cl
HCN

C O

Acid mandelic

HO C CN

CH2 Cl

CH2 CN
2 KCN

H2O

HO C CN

CH2 Cl

CH2 COOH

CH2 CN

HO C COOH
CH2 COOH
Acid citric

CH2 CH2
O

HCN

HO CH2 CH2 CN
-Hidroxipropionitril

H2O

HO CH2 CH2 COOH

Acid -hidroxipropionic

5. Reacia Reformatsky- -hidroxiacizi

Br CH2 COOR

+ BrZnCH2

Zn

BrZnCH2 COOR
O ZnBr

COOR

OH

H2O

CH2 COOR

-Zn(OH)Br

CH2 COOR

6. Oxidarea acizilor carboxilici nesaturai

HOOC

COOH

COOH

H
C

KMnO4

2 HO

HO C H
COOH

Acid fumaric

Acid (+)-tartric

COOH

COOH

H C OH

COOH
HO C H
H C OH
COOH
Acid (-)-tartric

COOH

KMnO4

H C OH

HO C H

2 HO

H C OH

HO C H

COOH

Acid maleic

COOH

COOH
Acid mezo-tartric

7. Metode biochimice
Fermentatie de zaharuri cu diverse tulpini de Lactobacillus
si Streptococcus lactis

Acid (S)-(-)- lactic

Fermentatie de zaharuri cu Aspergillus niger

Acid citric

 Reactivitate
1. Eliminare de ap

-hidroxiacizi
CH3 CH OH

H3C

CH3

HOOC CH CH3

COOH

OH
Acid lactic

Lactida

- Formare de polimeri- acid polilactic- biodegradabil

 -hidroxiacizi

HO CH2 CH2 COOH

Acid -hidroxipropionic

CH3 CH CH2 COOH

OH

-H2O

-H2O

Acid -hidroxibutiric

CH2 CH COOH
Acid acrilic

H3C CH CH COOH
Acid crotonic

HOOC CH CH2 COOH

OH

-H2O

HOOC CH CH COOH

Acid malic

Acid fumaric

OH
-H2O

CH2 COOH
Acid 1-ciclohexenilacetic

CH2 COOH
Acid 1-ciclohexanol
acetic

-H2O

CH COOH
Acid ciclohexilidenacetic

 - i -hidroxiacizi - formare de lactone

-lactonele sunt mai stabile dect -lactonele

Aroma de piersica

Aroma de cocos

 acidul citric

CH2 COOH
HO C COOH

CH2 COOH
H2SO4
-HCOOH

C O

CH3
C O

-2 CO2

CH2 COOH

CH2 COOH

Acid citric

Acid acetondicarboxilic

CH3
Acetona

Distilare uscata

CH2 COOH
HO C COOH
CH2 COOH
Acid citric

CH2

CH COOH
-H2O

C COOH
CH2 COOH
Acid aconitic

-CO2

CH CO
CO

-H2O

CH2 CO
Anhidrida
itaconica

O + C

CO

CH3
Anhidrida
citraconica

In organismele aerobe ciclul acidului citric (ciclul Krebs) este o parte a

cii metabolice de conversie a carbohidratilor, proteinelor si grasimilor
genereaza CO2 si apa

IV.2. Acizi fenolici

OH

OH

O
O

COOH

COOH

OH

HO

OH
Acid salicilic

COOH

COOH

Acid piperonilic

Acid galic

Acid 3-hidroxi-2-naftoic

Preparare
1. Sinteza Kolbe-Schmidt
O-Na+
+ CO2

OH
125oC
6 at.

OH
COO-Na+

COOH
HCl

COO-Na+
OH

O-Na+

OH

220 C

CO2

Coloranti azoici

120 C

COO-Na+
acid 3-hidroxi-2-naftoic

NH2

NH2

CO2

topire
alcalina

2 NaOH

SO3H

NH2

NH2

SO3Na

Medicament anti TBC

p;t

OH
COOH

OH

PAS

Mecanism

OH
H

CO2

COO

COO

 Aplicatii
Medicamente
OH

OH

OH

CONH2

COOCH3

NH3

CH3OH

- CH3OH

Salicilamida

Salicilat de metil

COOH

O COCH3
COOH

Ac2O

Acid salicilic

Aspirina

Conservanti
Parabenii
Activitatea antimicrobian depinde de lungimea
catenei ataate crescnd n
ordinea: metil < etil < propil < butil